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21.
Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes 下载免费PDF全文
Dr. Mario Carrasco Natalia Curado Dr. Eleuterio Álvarez Dr. Celia Maya Dr. Riccardo Peloso Prof. Dr. Manuel L. Poveda Dr. Amor Rodríguez Prof. Dr. Eliseo Ruiz Prof. Dr. Santiago Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):6092-6102
The bis(hydride) dimolybdenum complex, [Mo2(H)2{HC(N‐2,6‐iPr2C6H3)2}2(thf)2], 2 , which possesses a quadruply bonded Mo2II core, undergoes light‐induced (365 nm) reductive elimination of H2 and arene coordination in benzene and toluene solutions, with formation of the MoI2 complexes [Mo2{HC(N‐2,6‐iPr2C6H3)2}2(arene)], 3?C6H6 and 3?C6H5Me , respectively. The analogous C6H5OMe, p‐C6H4Me2, C6H5F, and p‐C6H4F2 derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo2 complex precursors. X‐ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the MoI2 core, coordinating to each in an η2 fashion. In solution, the arene rotates fast on the NMR timescale around the Mo2‐arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron‐rich C?C bonds. 相似文献
22.
An inorganic compound formulated as K3.31(NH4)0.69[Se2Mo5O21]·2H2O has been synthesized by conventional solution method and characterized by scanning electron microscopy, IR, UV-Vis spectroscopies behaviors. The structure of the title compound has been determined from a single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P21/n, with a?=?9.9371(2) ?, b?=?23.3545(2) ?, c?=?10.5179(2) ?, β?=?114.12(3)°, V?=?2227.7(5) ?3 and Z?=?4. It was revealed that the Strandberg-type polyoxoselenomolybdate cluster can be considered as a ring formed by five distorted edge- and corner-sharing MoO6 octahedra, capped on both poles by a selenate pyramids sharing three vertices with the ring molybdenum centers. The Strandberg clusters are connected with ammonium ions and water molecules through hydrogen-bonding interactions which ensure the cohesion of the structure into a three-dimensional network. 相似文献
23.
24.
Successive action of α-bromoesters and organometallics on hydroximates constitute a good way to obtain - 5,6 dihydro-1,4,2 dioxazines. 相似文献
25.
Jouini Houda Mejri Imène Rhimi Baker Mhamdi Mourad Blasco Teresa Delahay Gérard 《Research on Chemical Intermediates》2021,47(7):2901-2915
Research on Chemical Intermediates - Fe–Cu–ZSM-5 and Ce–Fe–Cu–ZSM-5 solids prepared using solid-state ion exchange method (SSIE) were tested in the NH3–SCR of NO... 相似文献
26.
Magnetic Coupling Constants of Self‐Assembled CuII [3×3] Grids: Alternative Spin Model from Theoretical Calculations 下载免费PDF全文
Dr. Carmen J. Calzado Dr. Nadia Ben Amor Dr. Daniel Maynau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):8979-8987
This paper reports a theoretical analysis of the electronic structure and magnetic properties of a ferromagnetic CuII [3×3] grid. A two‐step strategy, combining calculations on the whole grid and on binuclear fragments, has been employed to evaluate all the magnetic interactions in the grid. The calculations confirm an S=7/2 ground state, which is in accordance with the magnetisation versus field curve and the thermal dependence of the magnetic moment data. Only the first‐neighbour coupling terms present non‐negligible amplitudes, all of them in agreement with the structure and arrangement of the Cu 3d magnetic orbitals. The results indicate that the dominant interaction in the system is the antiferromagnetic coupling between the ring and the central Cu sites (J3=J4≈?31 cm?1). In the ring two different interactions can be distinguished, J1=4.6 cm?1 and J2=?0.1 cm?1, in contrast to the single J model employed in the magnetic data fit. The calculated J values have been used to determine the energy level distribution of the Heisenberg magnetic states. The effective magnetic moment versus temperature plot resulting from this ab initio energy profile is in good agreement with the experimental curve and the fitting obtained with the simplified spin model, despite the differences between these two spin models. This study underlines the role that the theoretical evaluations of the coupling constants can play on the rationalisation of the magnetic properties of these complex polynuclear systems. 相似文献
27.
Influences of nanoparticles and chain length on thermodynamic and electrical behavior of fluorine liquid crystals 下载免费PDF全文
Ines Ben Amor Lotfi Saadaoui Abdulaziz N. Alharbi Talal M. Althagafi and Taoufik Soltani 《中国物理 B》2022,31(10):104202-104202
Hydrogen-bonded polar nematic liquid crystal series with the general formula nOBAF (n = 7—12) is studied. The mesomorphic characterization is demonstrated through differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The complexes with short alkyl chains (n=7, 8) present a wide nematic range and monotropic smectic F mesophase, whereas the longer alkyl chain (n=10—12) analogues show high melting and low clearing mesomorphic liquid crystals. The thermal range of the mesophase and the birefringence increase with chain length decreasing. Furthermore, the effect of the nanoparticles (LiNbO3) on the thermal and the electrical behavior of 8OBAF are investigated. The presence of LiNbO3 nanoparticles increases the conductivity and reduces the resistivity of the complex. 相似文献
28.
Markov Chain Monte Carlo (MCMC) methods may be employed to search for a probability distribution over a bounded space of function arguments to estimate which argument(s) optimize(s) an objective function. This search-based optimization requires sampling the suitability, or fitness, of arguments in the search space. When the objective function or the fitness of arguments vary with time, significant exploration of the search space is required. Search efficiency then becomes a more relevant measure of the usefulness of an MCMC method than traditional measures such as convergence speed to the stationary distribution and asymptotic variance of stationary distribution estimates. Search efficiency refers to how quickly prior information about the search space is traded-off for search effort savings. Optimal search efficiency occurs when the entropy of the probability distribution over the space during search is maximized. Whereas the Metropolis case of the Hastings MCMC algorithm with fixed candidate generation is optimal with respect to asymptotic variance of stationary distribution estimates, this paper proves that Barker’s case is optimal with respect to search efficiency if the fitness of the arguments in the search space is characterized by an exponential function. The latter instance of optimality is beneficial for time-varying optimization that is also model-independent. 相似文献
29.
Viviana Heguaburu Hugo do Carmo Florencia Parpal María Eugenia Amorós Andrés González 《Tetrahedron letters》2017,58(18):1738-1741
The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media. 相似文献
30.
Samiha SalmaouiFaouzi Sediri Néji GharbiChristian Perruchot Salah AeiyachIwona A. Rutkowska Pawel J. KuleszaMohamed Jouini 《Applied Surface Science》2011,257(19):8223-8229
Tungsten trioxide, unhydrated with hexagonal structure (h-WO3), has been prepared by hydrothermal method at a temperature of 180 °C in acidified sodium tungstate solution. Thus prepared h-WO3 has been characterized by X-ray diffraction (XRD) method and using electrochemical techniques. The morphology has been examined by scanning and transmission electron microscopies (SEM and TEM) and it is consistent with existence of nanorods of 50-70 nm diameter and up to 5 μm length. Cyclic voltammetric characterization of thin films of h-WO3 nanorods has revealed reversible redox behaviour with charge-discharge cycling corresponding to the reversible lithium intercalation/deintercalation into the crystal lattice of the h-WO3 nanorods. In propylene carbonate containing LiClO4, two successive redox processes of hexagonal WO3 nanorods are observed at the scan rate of 50 mV/s. Such behaviour shall be attributed to the presence of at least two W atoms of different surroundings in the lattice structure of h-WO3 nanorods. On the other hand, in aqueous LiClO4 solution, only one redox process is observed at the scan rate of 10 mV/s. The above observations can be explained in terms of differences in the diffusion of ions inside two types of channel cavities existing in the structure of the h-WO3 nanorods. Moreover, the material can be applied as active support for the catalytic bi-metallic Pt-Ru nanoparticles during electrooxidation of ethanol in acid medium (0.5 mol dm−3 H2SO4). 相似文献